Condensation products of polyht



Patented Sept. 7, 1948 UNl'I ED sTArEs PATENTOFFICE ammo oonnansanox rnonuo'rs or roamsurname naoxy WITH ALDEHYDES William B. Johnston, Stamford, Com, aoaignor Cyanamid to American Company, New York,

N. Y., acorporation of Maine No Drawing. Application Serial No. 413.

8 Claims. (c1. zoo-sow) This invention relates to new organic compounds and their preparation, particularly those such as are obtained by the condensation of aldehydes with polyhydroxy alkylamlnes.

I have discovered that polyhydroxy alkylamines may be reacted with aldehydes, preferably formaldehyde, to produce a new class of organic compounds. The polyhydroxy alkylamines which I employ include those such as 2'-amino-1,3-propane-diol, 2-amino-2-methyl-1,3-propane-dloi, 2- amino-2-methylol-1,3-propanediol [tris(hydroxy- 'methyDamino methane], 2-amino-2-ethyl-1,3-

propane-d101, 2 amino 2-ethylol-l,3-propanediol, 2-amino-2-isopropyl-l,3-propane-dlol, etc., which have the general formula OHzOH R-CNH:

CHzOH in which R is a member of the group consisting of H, alkyl and alkylol radicals. These compounds may be prepared in known manner by the action of aliphatic aldehydes on primary aliphatic nitroparaffins followed by the catalytic reduction of the nitrohydroxy compounds to the corresponding polyhydroxy alkylamine. Although I prefer to use formaldehyde in my process other aldehydes such as acetaldehyde, heptaldehyde, propionaldehyde, benzaldehyde', etc., may be employed.

The reaction whereby the compounds of the present invention areproduced may be brought about in most cases simply by mixing the polyhydroxy alkylamines with formalin. If it is slow it may be speeded up somewhat by gently warming but in most cases it will be found to proceed easily with the evolution of heat. The reaction may be illustrated by the following general equation:

om-o onion om R- -NH, 2011.0 R- N/. zmo

H.011 cm I m -o Although experimental evidence leads me to believe that the formula given hererepresents the most probable structure of my compounds I wish it to be understood that it is given primarily to October}, 1941, 852

' in the preparation of esters, drying oils, alkyd resins, etc. For example, a drying oil of excellent drying properties may be prepared by reacting my new compounds with unsaturated fatty acids. The reaction may be illustrated by the following equations in which the condensation product of tris (hydroxymethyl) amino methane and formaldehyde is reacted with soya bean fatty acids (RCOOH).

group in the above compound is apparently unstable and undergoes further changes the nature of which is not definitely known but which result in the splitting out of formaldehyde CHIOH CHzOH 9 OHIO CHiOH and also the possible elimination of a molecule of H20 CHlOH --N=CH| very likely trimerizes to form a closed ring struc ture. It should be understood, however, that the above equations represent merely a likely course of the reaction of my new compounds with fatty acids and they are given for'the purpose of illustrating how my new compounds may be utilized. Regardless of the mechanism of the reaction the reaction product of my compounds with various unsaturated fatty acids and mixtures thereof give drying oils which dry with great rapidity and yield hard films of great water resistance.

My invention will now be described in greater particularity in the following specific examples to which, however; it is not limited. Other condensation products may, of course, be prepared with modifications within the skill of the art.

Example 1 121 parts by weight (1 mole) of tris (hydroxymethyl) amino methane was dissolved in 162 parts by weight (2 moles) of aqueous 37% formalin at room temperature. The resulting solution was almost neutral in reaction indicating that most of the amino compound was reacted. Water was then removed by evaporation at room temperature and a crystalline solid obtained which was soluble in acetone and benzene. The product on analysis was found to contain 49.4% carbon, 7.4% hydrogen and 9.1% nitrogen. It had a melting point of 62-63 C. and a hydroxyl value of 372. From these data it appears that the compound has the probable structural formula V cm-o l CHI HOCHr- --N Hr-O which may be called 3,4-oxydimethyl-4-methylol oxazolidine.

The compound prepared above was reacted with the fatty acids of soya bean oil and linseed oil and the isomerized fatty acids of linseed oil to yield esters having exceptionally good drying qualities.

Example 2 was dried with a little NasBOe and the ether then.

, 4 evaporated to yield a mobile colorless liquid having a boiling point of 178-1890., freezing point of 5 C. and index of refraction of C. of

1.4558. The product was soluble in water and petroleum ether.

Example 3 119 parts by weight of 2-ethyl-2-arnino pro- 'panedlol-1,3 was mixed with 439 parts by weight of 37% formalin (162 parts CHsO). The heat of the reaction carried the reaction mixture to 80 C. after which it was cooled to room temperature y and extracted twice with ethyl ether. Theether moved by evaporation.

distilled under a vacuum of 1-2 mm. at which it extract was dried with NazSOs and the ether re- The product was then boiled at 75-'77 Cato yield a clear mobile liquid The product was made into a drying oil by heating with the fatty acids of linseed oil and gave an oil which air dried rapidly to give a good film resistant to both hot and cold water.

What I claim is: y

1. The condensation product of an aldehyde with a polyhydroxy alkylamine of the general formula onion R NHI HsOH where R is a member of the group consisting of H. alkyl and alkylol radicals said condensation product having the general formula:

in which R is as defined above and R is the residue of the aldehyde employed in the reaction. 2. The condensation product of formaldehyde with a polyhydroxy alkylamine of the general formula cmoa R-JJ-NH:

CHSOH where R is a member of the group consisting of H, alkyl and alkylol radicals said condensation product having the general formula:

Hr-O

in which R is as defined above.

3. A process of preparing condensation products of the general formula UHF-0 I OH:

Hr-O

in which R is a member of the group consisting of H, alkyl and alkylol radicals which comprises mixing formaldehyde with polyhydroxy alkylarnines of the general formula CHIOH I R--NB: 63:08

in which R is as above and allowing the mixture to react until the said condensation products have been formed.

v 4. A process of preparing condensation products of the general formula which comprises mixing formaldehyde with polyhydroxy alkyl amines of the general formula onion HOCHEC-Nllz onion and allowing the mixture to react until the said condensation products have been formed.

5. The condensation product of formaldehyde with a polyhydroxy alkylamine of the general formula onion C--NH:

in which R is an alkylol radical, said condensation product having the general formula in which R is as defined above.

6. The condensation product of formaldehyde with -a polyhydroxy alkylamine of the general formula cmon HO CHz-C-NH:

. HzOH said condensation product having the formula cm-o no CH:-C--N 7. The condensation product of formaldehyde with a polyhydroxy alkylamine of the general formula onion HO QHzCH:-$NH1 I onion said condensation product having the formula CHz-o J: CH2 HOCHzCHz- N /CH2 CHz-O REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,972,465 Ulrich et a1. Sept. 4, 1934 2,194,294 Cass Mar. 19, 1940 2,194,314 Maxwell Mar. 19, 1940 2,243,295 Susie May 27, 1941 2,247,106 Vanderbilt June 24, 1941 2,250,408 De Groote July 22, 1941 FOREIGN PATENTS Number Country Date 564,787 Germany Nov. 23, 1932 566,453 Germany Dec. 17, 1932 OTHER REFERENCES Industrial & Engineering Chemistry, Vanderbilt et al., vol. 32 (1940), pages 34 to 38. 

